CN109192954A - A kind of CNTs@MnO2Composite material and preparation method and application - Google Patents

A kind of CNTs@MnO2Composite material and preparation method and application Download PDF

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Publication number
CN109192954A
CN109192954A CN201811046816.2A CN201811046816A CN109192954A CN 109192954 A CN109192954 A CN 109192954A CN 201811046816 A CN201811046816 A CN 201811046816A CN 109192954 A CN109192954 A CN 109192954A
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China
Prior art keywords
cnts
mno
composite material
dopamine
nitric acid
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CN201811046816.2A
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Chinese (zh)
Inventor
曹康哲
刘会俏
李汪洋
任雪晴
王富贵
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Xinyang Normal University
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Xinyang Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to electrochemical material technical fields, disclose a kind of CNTs@MnO2Composite material, MnO in composite material2For the δ-MnO with layer structure2, δ-MnO2Growth in situ forms CNTs@MnO in the outer surface CNTs2Composite material.When as lithium ion battery negative material in application, due to carbon nanotube electric conductivity and MnO2Space in nanoscale twins provides cushion space for the volume expansion of electrochemical reaction process, to improve CNTs@MnO2The specific capacity and cyclical stability of composite material negative electrode material.The invention also discloses CNTs@MnO2The preparation method of composite material, this method can be completed, ambient operation without complicated equipment in common reaction vessel, and securely and reliably, no toxic or polluted gas generates, and environmentally protective, low energy consumption, convenient for amplification production.

Description

A kind of CNTs@MnO2Composite material and preparation method and application
Technical field
The invention belongs to electrochemical material technical fields, are related to a kind of CNTs@MnO2Composite material and preparation method and Using.
Background technique
Lithium ion battery in today's society using extremely wide.However, as people need long cruising ability battery That asks quicklys increase, and the battery for developing high-energy density is extremely urgent.The promotion of performance of lithium ion battery, largely according to Rely the improvement in electrode material.Currently used negative electrode material is usually graphite, lower (the 374 mAh g of theoretical specific capacity-1), It is difficult to the requirement for meeting people to high energy density cells.Transition metal oxide MnO2As the negative electrode material of battery, have 1232 mAh g-1Theoretical specific capacity, and cheap, resourceful, no pollution to the environment.But MnO2Electron conduction compared with Difference is unfavorable for the promotion of its chemical property.In conventional method, have MnO2It is compound with the preferable material progress of electric conductivity, but Due to cannot achieve coming into full contact with for the two, cause performance boost not ideal enough.
Currently, having accomplished in many ways nanometer MnO2Preparation, such as solid phase method, the precipitation method, hydrothermal synthesis method, colloidal sol Gel method, microemulsion method etc., but MnO in these methods2Synthesis technology it is more complicated, take a long time and need to use high temperature and add Hot equipment can quickly prepare MnO at room temperature2And its report of composite material almost without.
Summary of the invention
The purpose of the present invention is to provide a kind of CNTs@MnO2Composite material improves MnO2The ratio of nanometer sheet negative electrode material Capacity and cyclical stability, solve MnO2The low problem of conductivity.
Another object of the present invention is to provide a kind of CNTs@MnO2The preparation method of composite material, ambient operation, safety Reliably, environmentally protective, low energy consumption, convenient for amplification production.
A further object of the present invention is to provide a kind of CNTs@MnO2Composite material is in lithium ion battery negative material Using.
To achieve the above object, the invention adopts the following technical scheme:
The present invention provides a kind of CNTs@MnO2Composite material, MnO in the composite material2For the δ-MnO with layer structure2, δ-MnO2Growth in situ forms CNTs@MnO in the outer surface CNTs2Composite material.
The present invention also provides a kind of above-mentioned CNTs@MnO2The preparation method of composite material, comprising the following steps:
Step 1: by diameter be 20 ~ 40 nm CNTs ultrasonic disperse in nitric acid solution, flow back 6 h, be cooled to room temperature, be centrifuged, It is first washed with deionized to neutrality, is then washed with ethyl alcohol, be dried in vacuo 12 h at 40 DEG C to get to through nitric acid treatment CNTs；
Step 2: will be scattered in the Tris-HCl of pH=8.5, ultrasonic disperse 1h, be added through the CNTs that nitric acid treatment is crossed in step 1 Dopamine, stir 12 h, 5min is centrifuged under the revolving speed of 10000 r/min, respectively with deionized water washing three times, ethyl alcohol wash one It is secondary, it is dried in vacuo the h of 8 h ~ 10 at 40 DEG C, obtains the CNTs of cladding poly-dopamine；
Step 3: the CNTs for coating dopamine in step 2 being re-dispersed into water, excessive KMnO is added4, stir at room temperature It after the h of 0.1 h ~ 0.5, filters, is dried in vacuo the h of 8 h ~ 10 at 40 DEG C to get CNTs@MnO is arrived2Composite material.
Further, the temperature of reflux described in step 1 is 120 DEG C.
Further, the mass ratio of the CNTs crossed through nitric acid treatment and dopamine is (0.5 ~ 2): 1.
The present invention also provides a kind of above-mentioned CNTs@MnO2Application of the composite material in lithium ion battery negative material.
Compared with prior art, the beneficial effects of the present invention are:
1. CNTs@MnO of the present invention2Composite material, wherein MnO2For the δ-MnO with layer structure2, δ-MnO2Growth in situ exists The outer surface CNTs forms CNTs@MnO2Composite material；When as lithium ion battery negative material, due to the conduction of carbon nanotube Property and MnO2Space in nanoscale twins provides cushion space for the volume expansion of electrochemical reaction process, to improve CNTs@MnO2The specific capacity and cyclical stability of composite material negative electrode material, solve MnO2The low problem of conductivity.
2. CNTs@MnO of the present invention2The preparation method of composite material, first by dopamine in CNTs surface aggregate, using poly- more The reproducibility of bar amine, by KMnO4It is reduced into δ-MnO2, and Mn and O element is evenly distributed in outer layer, C element is only distributed in interior Layer, this illustrates that the poly-dopamine on the surface CNTs participates in reacting completely, so that generating MnO in CNTs surface in situ at room temperature2 Nanometer sheet；This method can be completed, ambient operation without complicated equipment in common reaction vessel, and securely and reliably, nothing has Poison or polluted gas generate, and environmentally protective, low energy consumption, convenient for amplification production.
Detailed description of the invention
Fig. 1 is the XRD diagram for the CNTs that the present invention is crossed through nitric acid treatment.
The TEM figure that Fig. 2 is the CNTs that the present invention is crossed through nitric acid treatment.
Fig. 3 be the present invention cladding poly-dopamine before and after CNTs respectively with KMnO4The XRD comparison diagram of product after reaction.
Fig. 4 is CNTs@MnO prepared by the present invention2TEM figure of the composite material under different amplification.
Fig. 5 is CNTs@MnO prepared by the present invention2The distribution diagram of element of composite material.
Fig. 6 is CNTs@MnO2Composite material, MnO2Nanometer sheet and CNTs negative electrode material are in 500 mA g-1Under current density Cyclical stability figure.
Specific embodiment
The following examples are intended to illustrate the invention, but is not used to limit the scope of protection of the present invention.Unless otherwise specified, real Apply the conventional means that technological means used in example is well known to those skilled in the art.Test method in following embodiments, such as It is conventional method without special instruction.Test reagent in following embodiments is unless otherwise instructed conventional reagent.
CNTs model L-MWNT-2040 in following embodiments is purchased from Nanometer Port Co., Ltd., Shenzhen.
Embodiment one
A kind of CNTs@MnO2The preparation method of composite material, comprising the following steps:
Step 1: by diameter be 20 ~ 40 nm 0.5 g CNTs ultrasonic disperse in 100 mL, 6 mol L-1Nitric acid solution in, Flow back 6 h at 120 DEG C, is cooled to room temperature, and centrifugation is first washed with deionized to neutrality, is then washed with ethyl alcohol, at 40 DEG C 12 h are dried in vacuo to get to the CNTs through nitric acid treatment, XRD diagram as shown in Figure 1, transmission electron microscope figure (TEM) such as Shown in Fig. 2.As seen from Figure 1, CNTs crystallinity is preferable, and the diffraction maximum for being 26.3 °, 43.1 ° and 54.3 ° in 2 θ values is right respectively Answer (002), (100) and (004) crystal face.As seen from Figure 2, the surface CNTs is smooth, without attachment.
Step 2: dispersing the 50 mg CNTs crossed through nitric acid treatment in the Tris-HCl of 50 mL, pH=8.5, ultrasound point 1 h is dissipated, 50 mg dopamines are added, 12 h is stirred, 5min is centrifuged under the revolving speed of 10000 r/min, uses deionized water respectively Washing three times, ethyl alcohol wash once, 8 h are dried in vacuo at 40 DEG C, obtain coat poly-dopamine CNTs.
Step 3: the CNTs for coating dopamine in step 2 being re-dispersed into water, the excessive KMnO of 50mg is added4, room It after 0.3 h of the lower stirring of temperature, filters, is dried in vacuo 8 h at 40 DEG C to get CNTs@MnO is arrived2Composite material.
Referring to FIG. 3, Fig. 3 show cladding poly-dopamine before and after CNTs respectively with KMnO4XRD pairs of product after reaction Than figure.Fig. 3 and Fig. 1 is compared it is found that being coated with the CNTs and KMnO of poly-dopamine4Product after reaction 2 θ values be 24 ° with 37 ° of diffraction maximum respectively corresponds δ-MnO2(002) and (200) crystal face, the XRD diagram of CNTs without coating dopamine do not have It changes, shows the poly- bar amine for being coated on the surface CNTs and KMnO4δ-MnO is generated after reaction2。
Referring to FIG. 4, Fig. 4 shows the CNTs and KMnO of cladding poly-dopamine4Reaction product CNTs@MnO2Composite material TEM figure under different amplification, wherein the amplification factor of Fig. 4-a is 200nm, and the amplification factor of Fig. 4-b is 20nm.By scheming 4 can see, and the surface CNTs coats one layer of MnO2Nanometer sheet.
Referring to FIG. 5, Fig. 5 shows CNTs@MnO2The distribution diagram of element of composite material.From Fig. 5 it can also be seen that Mn and O element is evenly distributed in outer layer, and C element is only distributed in internal layer, this illustrates that the poly-dopamine on the surface CNTs participates in reacting completely, By KMnO4It is reduced into δ-MnO2, so that generating MnO in CNTs surface in situ at room temperature2Nanometer sheet has obtained CNTs@MnO2 Composite material.
Embodiment two
A kind of CNTs@MnO2The preparation method of composite material, comprising the following steps:
Step 1: by diameter be 20 ~ 40 nm 0.5 g CNTs ultrasonic disperse in 100 mL, 6 mol L-1Nitric acid solution in, Flow back 6 h at 120 DEG C, is cooled to room temperature, and centrifugation is first washed with deionized to neutrality, is then washed with ethyl alcohol, at 40 DEG C 12 h are dried in vacuo to get the CNTs through nitric acid treatment is arrived.
Step 2: dispersing the 25 mg CNTs crossed through nitric acid treatment in the Tris-HCl of 50 mL, pH=8.5, ultrasound point 1 h is dissipated, 50 mg dopamines are added, 12 h is stirred, 5 min is centrifuged under the revolving speed of 10000 r/min, use deionized water respectively Washing three times, ethyl alcohol wash once, 8 h are dried in vacuo at 40 DEG C, obtain coat poly-dopamine CNTs.
Step 3: the CNTs for coating dopamine in step 2 being re-dispersed into water, 50 mg KMnO are added4, at room temperature It after stirring 0.1 h, filters, is dried in vacuo 8 h at 40 DEG C to get CNTs@MnO is arrived2Composite material.
Embodiment three
A kind of CNTs@MnO2The preparation method of composite material, comprising the following steps:
Step 1: by diameter be 20 ~ 40nm 0.5g CNTs ultrasonic disperse in 100 mL, 6 mol L-1Nitric acid solution in, Flow back 6 h at 120 DEG C, is cooled to room temperature, and centrifugation is first washed with deionized to neutrality, is then washed with ethyl alcohol, true at 40 DEG C Sky dries 12 h to get the CNTs through nitric acid treatment is arrived.
Step 2: dispersing the 100mg CNTs crossed through nitric acid treatment in the Tris-HCl of 50 mL, pH=8.5, ultrasound point 1h is dissipated, 50mg dopamine is added, 12 h is stirred, 5 min is centrifuged under the revolving speed of 10000 r/min, uses deionized water water respectively Wash three times, ethyl alcohol wash once, be dried in vacuo 10h at 40 DEG C, obtain cladding poly-dopamine CNTs.
Step 3: the CNTs for coating dopamine in step 2 being re-dispersed into water, the excessive KMnO of 50mg is added4, room It after 0.5 h of the lower stirring of temperature, filters, is dried in vacuo 10 h at 40 DEG C to get CNTs@MnO is arrived2Composite material.
Example IV CNTs@MnO2The application of composite material
Use conductive black Super-p-Li for conductive agent, hydroxymethyl cellulose (CMC) is binder, the composition of Electrode Negative piece For active material CNTs@MnO2Composite material, Super-p-Li, CMC, three's mass ratio are 7:2:1.It weighs in proportion above-mentioned each The total 30mg of ingredient, is put into mortar and is fully ground, and suitable water is added as dispersing agent, is ground into uniform slurries.It is applied with machinery Cloth method by made slurry copper foil surface coating be about 100 μ m-thicks film, by 40 DEG C in a vacuum drying oven 8 ~ 10 h of drying Afterwards, the disk that copper foil is cut into 12 mm of diameter calculates the active material CNTs@MnO loaded on disk using difference assay2It is multiple Condensation material quality.CNTs@MnO is tested using CR2032 button cell mold2The storage lithium performance of composite material.In addition, by active Substance replaces with MnO respectively2Nanometer sheet and CNTs are tested as a comparison.
Referring to FIG. 6, Fig. 6 shows CNTs@MnO2Composite material, MnO2Tri- kinds of materials of nanometer sheet and CNTs are in 500 mA g-1Cyclical stability comparison diagram under current density.As seen from Figure 6, after circulation 50 weeks, CNTs@MnO2Composite material Specific capacity remains at 435 mAh g-1, hence it is evident that it is higher than MnO2The specific capacity of nanometer sheet and CNTs negative electrode material, shows the present invention The CNTs@MnO of preparation2When composite material is as lithium ion battery negative material, due to the electric conductivity and MnO of carbon nanotube2 Space in nanoscale twins provides cushion space for the volume expansion of electrochemical reaction process, to improve CNTs@MnO2 The specific capacity and cyclical stability of composite material negative electrode material, solve MnO2The low problem of conductivity.
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit The scope of the present invention processed to those of ordinary skill in the art certainly can be according to skill disclosed in this specification Art content makes other embodiments easily by way of replacing or changing, therefore all made in the principle of the present invention Changes and improvements etc., should be included in scope of the present invention patent.

Claims (5)

1. a kind of CNTs@MnO2Composite material, which is characterized in that MnO in the composite material2For the δ-with layer structure MnO2, δ-MnO2Growth in situ forms CNTs@MnO in the outer surface CNTs2Composite material.
2. a kind of CNTs@MnO2The preparation method of composite material, which comprises the following steps:
Step 1: by diameter be 20 ~ 40 nm CNTs ultrasonic disperse in nitric acid solution, flow back 6 h, be cooled to room temperature, be centrifuged, It is first washed with deionized to neutrality, is then washed with ethyl alcohol, be dried in vacuo 12 h at 40 DEG C to get to through nitric acid treatment CNTs；
Step 2: will be scattered in the Tris-HCl of pH=8.5 in step 1 through the CNTs that nitric acid treatment is crossed, 1 h of ultrasonic disperse adds Enter dopamine, stir 12 h, 5 min are centrifuged under the revolving speed of 10000 r/min, respectively with deionized water washing three times, ethyl alcohol It washes once, the h of 8 h ~ 10 is dried in vacuo at 40 DEG C, obtain the CNTs of cladding poly-dopamine；
Step 3: the CNTs for coating dopamine in step 2 being re-dispersed into water, excessive KMnO is added4, stir at room temperature It after the h of 0.1 h ~ 0.5, filters, is dried in vacuo the h of 8 h ~ 10 at 40 DEG C to get CNTs@MnO is arrived2Composite material.
3. a kind of CNTs@MnO according to claim 22The preparation method of composite material, which is characterized in that institute in step 1 The temperature for stating reflux is 120 DEG C.
4. a kind of CNTs@MnO according to claim 22The preparation method of composite material, which is characterized in that described through nitric acid The mass ratio of processed CNTs and dopamine is (0.5 ~ 2): 1.
5. a kind of CNTs@MnO described in claim 12Application of the composite material in lithium ion battery negative material.
CN201811046816.2A 2018-09-08 2018-09-08 A kind of CNTs@MnO2Composite material and preparation method and application Pending CN109192954A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106206065A (en) * 2016-09-14 2016-12-07 安徽师范大学 A kind of electrode material for super capacitor MnO2the preparation method of@PDA nano composite material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106206065A (en) * 2016-09-14 2016-12-07 安徽师范大学 A kind of electrode material for super capacitor MnO2the preparation method of@PDA nano composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KANGZHE CAO等: ""Encapsulating sulfur in δ-MnO2 at room temperature for Li-S battery cathode"", 《ENERGY STORAGE》 *

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